Asymmetric synthesis of bicyclo[4.3.1]decadienes and bicyclo[3.3.2]decadienes via [6 + 3] trimethylenemethane cycloaddition with tropones.
The cyanosubstituted trimethylenemethane donor undergoes palladium-catalyzed [6 + 3] cycloaddition with a variety of tropones to yield bicyclo[4.3.1]decadienes in excellent regio-, diastereo-, and enantioselectivity. Products of the Pd-TMM [6 + 3] cycloaddition participate in a thermal [3,3] sigmatropic rearrangement to yield bicyclo[3.3.2]decadienes in good yield.
Trost
Barry M
BM
Department of Chemistry, Stanford University, Stanford, California 94305-5080, USA. bmtrost@stanford.edu
McDougall
Patrick J
PJ
Hartmann
Olaf
O
Wathen
Peter T
PT
D001643:Bridged Bicyclo Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D002384:Catalysis; D003500:Cyclization; D007659:Ketones / Q000138:chemical synthesis / Q000737:chemistry; D008055:Lipids / Q000138:chemical synthesis* / Q000737:chemistry; D008697:Methane / Q000031:analogs & derivatives* / Q000737:chemistry; D010165:Palladium / Q000737:chemistry; D011090:Polyenes / Q000138:chemical synthesis* / Q000737:chemistry; D014334:Tropolone / Q000031:analogs & derivatives* / Q000737:chemistry
D001643:Bridged Bicyclo Compounds; D007659:Ketones; D008055:Lipids; D011090:Polyenes; C522820:trimethylenemethane; D010165:Palladium; D014334:Tropolone; C003730:tropone; D008697:Methane